CN109072490A - Biodegradable Fypro, the polyamide article for obtaining the method for such fiber and being made from it - Google Patents

Biodegradable Fypro, the polyamide article for obtaining the method for such fiber and being made from it Download PDF

Info

Publication number
CN109072490A
CN109072490A CN201680084979.2A CN201680084979A CN109072490A CN 109072490 A CN109072490 A CN 109072490A CN 201680084979 A CN201680084979 A CN 201680084979A CN 109072490 A CN109072490 A CN 109072490A
Authority
CN
China
Prior art keywords
polyamide
biodegradable
fypro
reagent
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201680084979.2A
Other languages
Chinese (zh)
Inventor
R.雷东多博纳尔迪
G.戈尔斯古
P.韩苏帕克
R.麦克瑞特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Brasil SA
Original Assignee
Rhodia Poliamida e Especialidades Ltda
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=56014643&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN109072490(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Rhodia Poliamida e Especialidades Ltda filed Critical Rhodia Poliamida e Especialidades Ltda
Publication of CN109072490A publication Critical patent/CN109072490A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/12—Physical properties biodegradable

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyamides (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Nonwoven Fabrics (AREA)
  • Woven Fabrics (AREA)

Abstract

The present invention relates to a kind of biodegradable Fypros.The method for obtaining such fiber that invention further discloses a kind of and the product being made from it.Biodegradable Fypro of the invention can be obtained by adding biodegradable reagent in the melt-spun extrusion process of specific polyamide as described below.

Description

Biodegradable Fypro, for obtain such fiber method and by Its manufactured polyamide article
Abstract
The present invention relates to a kind of biodegradable Fypros.Invention further discloses one kind for obtaining such fibre The method of dimension and the product being made from it.Biodegradable Fypro of the invention can be by as described below Biodegradable reagent is added in the melt-spun extrusion process of specific polyamide to obtain.
Background technique
Sustainability, shorter life cycle, low environmental impact, renewable resource and Green Chemistry are to instruct next-generation material The new principle of material, product and technological development.Making great efforts to develop sustainable product, these sustainable products more and more in the whole world It is biodegradable, and is frequently made and has as far as possible the life cycle of much shorter by renewable resource (biology base) It is influenced with environment.
Biodegradable polymer is developed and has been commercialized recently, polymer, polylactic acid (PLA) such as based on starch, Poly- (lactic acid-co-glycolic acid) (PLGA), poly (propylene carbonate) (PPC), polycaprolactone (PCL), polyhydroxyalkanoates (PHA), Chitosan, glutelin, polyester such as poly butylene succinate (PBS), poly adipate succinic acid ester (PBA), poly-succinic-oneself two Sour butanediol ester, poly-succinic-decanedioic acid butanediol ester or polybutylene terephthalate (PBT)-are total to adipate ester.
Several trials have been carried out generally to enhance the biodegrade of polymer, for example, by polymer with can biology The polymer of degradation such as PLA, PVA, starch, natural fiber or biodegradable polyester blend, or by polymerizeing and/or squeezing Combine biodegradable additive so that they are biodegradable during out, such as oxygen-containing biodegradable by adding Additive, hydroperoxides, microorganism, prodegradant and " chemical inhibitor " additive.Since oxygen-containing biodegradable adds Add agent and prodegradant to accelerate light degradation and oxygen degradation, thus they tend to the machinery that polymer is reduced during its service life and Chemical characteristic.In addition, they are mainly made of transition metal, to cause ecotoxicity problems to environment.Therefore, they are uncomfortable It shares in textile application.
In addition, polymer such as PLA, PHB, PHA, polymer based on starch etc. due to its low melting point, low hydrolytic resistance, compared with High light and heat degradation and high mechanically and chemically characteristic cannot be provided, and they or it is brittle and water-soluble.Therefore, They do not provide enough characteristics for textile application, and tend to lose their machinery during the service life of textile fabrics Characteristic.In addition, natural biological base and highly biodegradable fiber such as cotton, wool and silk do not provide synthetic fibers and are provided Desired characteristic, such as durability, intensity and thermoplastic behavior.
This is why there is the demand for the biodegradability for increasing polymer, especially polyamide (since it goes out The mechanically and chemically characteristic of color).
For the polyamide in textile goods such as underwear, gym suit, easy dress and nightwear (in particular upon fiber and yarn Line) commercial interest widely increase because they are in easy nursing, fast dry characteristic, high-durability, excellent physics spy Advantage in terms of property, wearability, the hygroscopicity of balance, good elasticity, brightness, comfort level and pliability.Polyamide is (also referred to as Nylon) it is the linear condensation object being made of the repetition major key of amide group.Fypro usually passes through melt-spun and extrudes production And it can be obtained in the form of staple fiber, tow, monofilament, multifilament, flat or Texturized (texturized).Polyamide is Semicrystalline polymer.Amide group-(- CO-NH-)-hydrogen bond is provided between chain between polyamide molecule, to provide under high temperature High intensity, the toughness under low temperature, wear-resistant and abrasion, low-friction coefficient and good chemical resistance.These characteristics are So that polyamide becomes one of strongest in all obtainable staple fibres.However, polyamide and biology based on fossil Based polyamide usually require many decades could processing when complete biodegradable.According to Environmental Protection Department (EPA), traditional polymer It is biodegradable in refuse landfill and compost environment in 30 to 50 years.
2 842 406 A1 of EP is disclosed by introducing amino acid (such as glycine) in the course of the polymerization process come modified polyamide The alternative solution of fiber.The disadvantages of the method are as follows its variation (such as molecular weight, viscosity, anti-due to polymer in the course of the polymerization process The significant decrease of Zhang Qiangdu, elongation) and lead to mechanical degradation.2 842 406A1 of EP, which also shows to work as, is exposed to outdoor conditions When product (glass cutting wires) performance and durability reduce.
Another method, which has been reported by the way that polyamide to be blended with polyvinyl alcohol (PVA) or PLA, increases the life of polyamide Object degradability, as shown in 1490443 A of CN.But need a large amount of PLA (such as > 50%wt).Additionally, it is often necessary to phase Miscible agents are polyamide and PLA to be blended by squeezing out.
Therefore, current method is tended to change mechanically and chemically characteristic, to change the dyeing characteristic of textile fabrics.It Also show biological degradability in outdoor conditions (such as light degradation) and need the additive of higher amount.Therefore, they It is not successfully applied in textile fabrics.
In view of the foregoing, a kind of biodegradable polyamide of excellent characteristics with for textile application is needed Fiber.
Therefore, an object of the present invention is to provide a kind of Fypro and what is be made from it has increased biology drop Solve the product of rate.The Fypro should keep the characteristic of original polyamide, as viscosity (IVN), amino end group (ATG), Carboxyl end groups (CTG) and mechanical property, to retain polyamide characteristic needed for textile application.
In other words, the present invention is directed to find for obtaining the biodegradable Fypro for being used for textile fabrics application Solution.The chemistry and mechanical property that such Fypro should keep the service life of textile fabrics to need, and therefore Biodegradability only should be just shown when contacting with processing environment.
The object of the invention is also to provide a kind of methods for obtaining such biodegradable Fypro, and Biodegradable rate is clearly demonstrated by standard method of test, specific time range and processing approach.Advantageously, originally What invention should propose to have good mechanical properties and shelf life be both biology base and biodegradable polyamide it is fine Dimension.
Summary of the invention
Therefore the present invention provides a kind of biodegradable Fypro, and the polyamide fiber includes:
Polyamide at least 4% hygroscopicity increment (delta),
Biodegradable reagent.
In fact, it has been surprisingly found that using specific polyamide (it is characterized in that with 4% minimum hygroscopicity Increment) combine with biodegradable reagent and greatly accelerates the biodegrade of polyamide article to the journey for substantially reducing its environment and influencing Degree, without negatively affecting its desired textile characteristic and shelf life.A key property of the invention is resulting Fypro shows desired mechanical property identical with the biodegradable product of reagent is free of, and has and be free of life Object is degraded product effectively similar shelf life of reagent, and when treated, can be at least partly by almost institute on the earth The anaerobic and aerobic microbiologic population for having place common is metabolized to inertia biomass.
The present invention also aims to a kind of methods for obtaining the biodegradable Fypro, wherein in melt-spun Biodegradable reagent is introduced into the Fypro during extrusion.
In addition, it includes such as above and below to define in following paragraph the invention proposes a kind of polyamide article Biodegradable Fypro；And a kind of method for obtaining such polyamide article, wherein of the invention is poly- Nylon passes through Texturized, stretching, warping (warping), knitting, braiding, non-woven processing, clothes manufacture or combinations thereof And change.
Then, another object of the present invention is that the polyamide of the hygroscopicity increment at least 4% and biodegrade try Agent is combined to improve the purposes of the biodegradability characteristic of polyamide prepared therefrom.
Specific embodiment
Definition
Statement " Fypro " in the sense of the present invention is the generic term for including the following product being spun into: fiber, Monofilament, multifilament and yarn." polyamide article " according to the present invention be it is transformed or processing Fypro and including short Fiber, any short flannel or any textile composition, especially fabric and/or clothes made of Fypro.Following In explanation, term " fiber (fiber) ", " yarn (yarn) " and " long filament (filament) " can be used indistinguishably, without Change meaning of the present invention.
Term " biodegradation rate " refers to the time of polyamide article biodegrade to specific degrees.For example, in 30 days 5% biodegradation rate means the biogas (CO of discharge2+CH4) account for sample original carbon content by weight 5%. Biodegradation rate is measured according to ASTM D5511 testing standard.
Term " hygroscopicity increment " be under 30 DEG C and 90% relative humidity (RH) for 24 hours after polyamide hydroscopicity with 20 DEG C and 65% relative humidity (RH) under for 24 hours after polyamide hydroscopicity between difference.By the way that polyamide is dry at 105 DEG C It 2 hours, is placed it in above-mentioned two temperature and humidity condition later and calibrates the hydroscopicity of polyamide.
For example, following test is enough to measure hygroscopicity increment:
About 2 grams of polyamide are placed in weighing bottle, and 2 hours dry at 105 DEG C.Then the weighing bottle is weighed (weight W3).Then the weighing bottle is put into the climatic chamber under 20 DEG C and 65%RH 24 hours.The weight of sample is measured again (weight W1).Then the weighing bottle is put into the climatic chamber under 30 DEG C and 90%RH 24 hours.The weight of sample is measured again (weight W2).
Hygroscopicity increment is measured by following equation:
MR1=(W1-W3)/W3,
MR2=(W2-W3)/W3.
Pass through following acquisition hydroscopicity difference (hygroscopicity increment=Λ MR):
Λ MR=MR2-MR1.
Term " biodegradable reagent " is understood to mean that the concentrate of biodegradable transformation additive, usually with The form of liquid, solid or powder masterbatch uses.Term " masterbatch " refers to the multifunctional additive for lubricating oils in polymer substrate, most common Be pellet form.Masterbatch for introducing the additive into polymer in process, to obtain higher dispersibility And homogenieity.
Biodegradable Fypro
Polyamide at least 4% hygroscopicity increment
The fatty polyamide that the polyamide is made of AB and/or AABB type.It is advantageously selected from by the following terms group At group: polyamide 4, polyamide 4.6, polyamide 4.10；Polyamide 5.X, X are from 4 to 16 integers；Polyamide 6, polyamide 6.6, polyamide 6 .9, polyamide 6 .10；Polyamide 6 .12；Polyamide 10.10；Polyamide 10.12；Polyamide 11；Polyamide 12；Polyamide 12.12；And its mixture, on condition that these polyamide are modified if necessary to reach at least 4% hygroscopicity Increment.
Above-mentioned polyamide is well known in the art and is commercially available.They can pass through commercially available diacid and two The polycondensation of the mixture of amine monomers or its salt obtains.The diamines and diacid of polyamide AABB type belong to the group of following item: four methylenes Base diamines (1,4- diaminobutane or putrescine), hexamethylene diamine (1,6- hexamethylene diamine), ten dimethylene diamines (1,12- bis- Aminododecane), adipic acid (adipic acid), azelaic acid (azalaic acid), decanedioic acid (sebacic acid), heneicosanedioic acid, dodecane two Acid.The monomer of polyamide AB type belongs to the group of the following terms: caprolactam, 11- amino undecanoic amide, lauric lactam or laurel Lactams.
Polyamide 5.X is made of five methylene diamine and one or more aliphatic dicarboxylic acids of raw material.Potential binary carboxylic Acid is listed as follows: succinic acid (succinic acid), glutaric acid (glue acid), adipic acid (adipic acid), pimelic acid (jambulol), suberic acid are (soft Wood acid), azelaic acid (azalaic acid), decanedioic acid (sebacic acid), heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, the tetradecane Diacid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid).All these diacid are all commercially available.
Polyamide 5.X has the advantages that be manufactured according to ASTM6866 by biomass.Since five methylene diamine can also To be prepared according to ASTM6866 from living resources, obtained polyamide can be at least 40% biological source and at most 100% From living resources.
When needing to realize at least 4% hygroscopicity increment, polyamide can be chemically or physically modification.When being changed When learning modified, polyamide can be by being added hydrophilic modifier, such as water-soluble polymeric image polyvinylpyrrolidone, sulfonate pole Property group such as organic sulfonic acid；By being copolymerized the polyamide and ethylene oxide group or polyethers amine groups；By increasing amorphous area The ratio in domain carries out chemical modification.When carrying out physical modification, polyamide, which usually passes through, increases fiber and therefore water suction table The surface area in face, such as with the fibre structure for possessing high porosity and capillarity, to carry out physical modification.Advantageously, gather Amide can be by adding hydrophilic modifier, such as water-soluble polymer such as polyvinylpyrrolidone, and sulfonate polar groups are such as Organic sulfonic acid；Or it is modified by being copolymerized the polyamide with ethylene oxide group or polyethers amine groups.
The example for needing the polyamide of this modification is polyamide 4, polyamide 4.6, polyamide 4.10；Polyamide 5.10； Polyamide 6, polyamide 6 .6, polyamide 6 .9, polyamide 6 .10；Polyamide 6 .12；Polyamide 10.10；Polyamide 10.12；It is poly- Amide 11；Polyamide 12；Polyamide 12.12；And its mixture.
Particularly preferred polyamide is polyamide 5.6.In fact, the first polyamide 5.6 does not need to be modified to reach 4% minimum hygroscopicity increment, then when compared with conventional polyamide 6.6, which is shown and biodegradable reagent Positive cooperativity.In addition, according to ASTM D6866 testing standard according to measurement, which is biology base.
Polyamide 5.6 (nylon 5.6) or poly- (pentamethylene adipamide) is original by five methylene diamine and adipic acid Material preparation.
The content of the amino end group (ATG) for the polyamide that the present invention uses is advantageously from 25 to 60 equivalents/ton, and carboxylic The content of cardinal extremity base (CTG) is advantageously from 45 to 90 equivalents/ton.Those amino/carboxyl end groups content is according to hereafter testing The method explained in part measures.
Preferred polyamide 5.6 can have within the scope of 100 to 200ml/g, the viscosity preferably between about 120 and 170 Index (IVN).The IVN is measured according to the standard ISO 307 hereafter explained in experimental section.
Particularly preferred polyamide 5.6 according to the present invention with from 138 to 142 IVN (Viscosity Index) and from 38 to 42 ATG (amine end groups).
The hygroscopicity increment minimum 4%, advantageously from 4% to 10% of polyamide according to the present invention and more preferably from 5% to 8% variation.
Biodegradable reagent
Polymer of the biodegradable transformation additive commonly used in increase with very slow biodegradation rate Biodegradation rate.It is used for several method recently, such as uses oxygen-containing biodegradable additive, biodegradable Polymer and prodegradant.
Oxygen-containing biodegradable additive is claimed through oxidation and biodegradable combination degradation.In carbochain polymer Oxygen is introduced in main chain and results in functional group, and such as carboxylic acid or hydrogen carboxylic acid, ester and aldehyde and alcohol, these functional groups increase polymer Hydrophily.Pass through light degradation and thermal degradation accelerated oxidation.Light degradation absorbs the formation with free radical by UV to obtain.
Prodegradant is to can speed up reacting and oxygen atom being integrated to adding in polymer chain for polymer and aerial oxygen Add agent.The prodegradant for reporting most is transition metal salt, such as iron, cobalt and manganese.They can be catalyzed hydroperoxides and resolve into Free radical.Other prodegradant additives include aliphatic ester, amide and dithiocarbamate transition metal salt (such as Manganese stearate, cobalt acetate, cobaltous octadecanate, copper oleate and ferric acetate)；Ferrocene；Metal oxide such as TiO2 and ZnO；Insatiable hunger With alcohol or ester；Benzophenone；Gamma-pyrone；Beta-diketon；Polyisobutene；Selected amine (such as hexamine, aminoguanidine)；Peroxidating Object and hydroperoxides.It is above-mentioned due to oxygen, light and heat degradation (this leads to the reduction of the characteristic during the service life of textile) Additive is not suitable for textile application.In addition, they not environmentally and to soil cause ecotoxicological problem.
On the other hand, biodegradable polymer is used to pass through fast degraded biologically and therefore leaves with high interface Area and the porous and spongelike structure of low structural strength and keep polymer biodegradable.Then polymer substrate is begun through Enzyme hits and degrades, and causes polymer fracture at more easily by the relatively small molecule of microbial digestion.The most common method is using base In the polymer of starch, polylactic acid (PLA), poly- (lactic acid-ethanol) copolymer (PLGA), poly (propylene carbonate) (PPC), gather oneself Lactone (PCL), polyhydroxyalkanoates (PHA), chitosan, glutelin, copolyesters or aliphatic-aromatic polyester such as poly-succinic fourth Diol ester (PBS), poly adipate succinic acid ester (PBA), poly-succinic-tetramethylene adipate, poly-succinic-decanedioic acid fourth two Alcohol ester or polybutylene terephthalate (PBT)-are total to adipate ester.Polytetramethylene glycol succinate-adipate ester unfortunately, needs altogether Higher amount is wanted to keep polymer biodegradable, it is also necessary to compatible and plasticizer additives.
In the present invention, biodegradable reagent is preferably based on " chemical inhibitor (chemo attractant) " additive. These additives attract them and providing food to microorganism.It can also include additional additive, such as sweller, carboxylic Acid, peculiar microorganism etc..
Sufficiently disclosed in the U.S. Patent Publication application 2008/0103232 of Lake et al. be suitable as it is of the invention Composition, method and the exemplary, non-limitative biodegrade reagent with biodegradable reagent on the way.The some of the patent mention It takes object and content to be incorporated herein by quoting mode, and can clearly show that for biodegradable reagent of the invention.
Biological poly amide of the invention is provided and biodegradable reagent is introduced into Fypro to biology The increased sensibility of degradation.Biodegradable reagent advantageously includes the masterbatch of additive, these additives include but unlimited In:
1. chemical inhibitor or chemotaxis (chemo taxis) compound
2. glutaric acid or derivatives thereof
3. having the carboxylic acid compound from the chain length of 5-18 carbon
4. biodegradable polymer
5. vector resin
6. sweller
In one embodiment, biodegradable reagent includes by cannot be by the sugar of bacterial metabolism, cumarin or furanone group At chemical inhibitor or chemotaxis reagent to attract microorganism.The example of furanone includes 3,5- dimethyl-penten alkenyl two (3H) furanone of hydrogen 2 isomer mixture, epoxy furans and N- acyl homoserine lactones, or combinations thereof.Sugar example include But it is not limited to galactolipin, galactolipin hydrochlorate, glucose, succinate, malate, aspartate, serine salt, fumaric acid Salt, ribose, acetonate, oxalacetate and other L- sugar structures and D- sugar structure.In a preferred implementation benefit, using just Chemotaxis agent, such as the polyethylene terephthalate pellet of fragrance not by the starch D- sugar of microbial metabolism or are inhaled Draw the furanone or any combination thereof of microorganism.In one aspect, furan ketone compound is being equal to or more than 0- by weight In the range of 20%.On the other hand, furan ketone compound is the 20%-40% by weight or by weight of total additive 40%-60% or by weight 60%-80% or by weight 80%-100%.
In another embodiment, which includes glutaric acid or derivatives thereof.In one aspect, glutaric acid Compound can be such as propyl glutaric acid, but not limited to this.Glutaric acid is equal to or more than 0- total additive by weight In the range of 20%.On the other hand, glutaric acid is the 20%-40% by weight or 40%- by weight of total additive 60% or 60%-80% by weight or 80%-100% by weight, by weight 20%-40%, 40%-60%, 60%-80% or 80%-100%.
In another embodiment, carboxylic acid compound is preferably hexadecanoic acid compound, and pressing in total additive Poidometer is equal to or more than in the range of 0-20%.On the other hand, hexadecanoic acid is the 20%- by weight of total additive 40% or 40%-60% by weight or 60%-80% by weight or 80%-100% by weight, by weight 20%-40%, 40%-60%, 60%-80% or 80%-100%.
In another embodiment, biodegradable reagent includes biodegradable polymer, the polymer belong to The group of lower items: polylactic acid, poly- (lactic acid-ethanol) copolymer, poly (propylene carbonate), polycaprolactone, polyhydroxyalkanoates, Chitosan, glutelin and one or more aliphatic/aromatic polyester, as poly butylene succinate, poly-succinic-oneself Succinate adipate, poly-succinic-decanedioic acid butanediol ester or polybutylene terephthalate (PBT)-adipate ester or its mixing Object.In a preferred embodiment, which is polycaprolactone polymer.The polycaprolactone polymer The group of the following terms: poly- e- caprolactone, polycaprolactone, poly- (lactic acid), poly- (glycolic), poly- (cream can be selected from but not limited to Acid-glycolic).The polycaprolactone polymer is in total additive in the range of being equal to or more than 0-20% by weight.? On the other hand, polycaprolactone be total biodegradable reagent 20%-40% by weight or 40%-60% by weight, Or 60%-80% by weight or 80%-100% by weight, by weight 20%-40%, 40%-60%, 60%-80% Or 80%-100%.
In another embodiment, vector resin is by compatible with polyamide chemistry and to allow additive to disperse any poly- Close object composition.Most preferably, vector resin is made of polyamide 6, polyamide 66 and its mixture, wherein additive is melted mixed It closes to form masterbatch pellet.Vector resin and masterbatch pellet help biodegradable additive being placed in biological poly nylon In to make its biodegradable in an uniform manner, to ensure biodegrade appropriate.
In another embodiment, sweller is by the sense organ sweller such as colloid of natural fiber, culture, cyclodextrin, poly- The composition such as lactic acid.Natural or artificial sense organ sweller be additive by weight be equal to or more than 0-20% in the range of. In one aspect, sense organ sweller is the 20%-40% by weight or 40%- by weight of total biodegradable reagent 60% or 60%-80% by weight or 80-100% by weight.
In a preferred embodiment, biodegradable reagent may include furan ketone compound, glutaric acid, hexadecanoic acid Compound, polycaprolactone polymer, sense organ sweller (natural fiber, the colloid of culture, cyclodextrin, polylactic acid etc.) and load The mixture of body resin.
In another embodiment, which further includes the micro- life that can digest polyamide article Object.In another embodiment, which further includes dipropylene glycol.In another embodiment, should Biodegradable reagent further includes soybean derivatives, such as soybean methyl ester.In another embodiment, the biodegrade Reagent further includes one or more for controlling the antioxidant of biodegradation rate.
These biodegradable reagents are known to the skilled in the art and can quotient as solid, liquid or powder masterbatch Purchase, such as fromLLC'sFrom enso Plastics Company (ENSO Plastics) "SR5300"；" EcoPure " from Bio TEC Environmental LLC (Bio-Tec Environmental)；From ECM biomembrane " the ECM masterbatch pellet " of company (ECM biofilms)；From biosphere Plastics Company (BiosPhere Plastic) "BioSphere"；" Enso Restore " from enso Plastics Company；" MECO1 " from Hybrid Green.
When the biodegrade reagent with by weight about the 1.0% to 5.0% of the total weight of the Fypro, preferably from about In the presence of 2.0% to 3.0% amount, biological poly nylon according to the present invention has higher biodegradation rate.Most Good mode is when biodegradable reagent, especially businessMasterbatch is with the total weight of the Fypro In the presence of by weight 1.5% to 2.5% amount.
It is believed that when the processing in the environment (such as bioactivity refuse landfill or anaeroic digestor) rich in microorganism When, which enhances other not biodegradable polyamide article by a series of chemistry and bioprocess Biodegradability.Biodegradation process starts from sweller, and when combining with heat and moisture, which makes polyamide molecule Structure expansion.Biodegradable reagent makes polyamide become the attractive food source of certain edaphons, promotes polyamides Amine is quickly consumed than the polyamide without biodegradable reagent.The combination for the bioactive compound hereinbefore mentioned is inhaled Draw microbe colony, pass through natural microbial procedure decomposition chemical bond and is metabolized polyamide.
Biodegradable reagent needs the effect of certain enzymes to start biodegradation process, therefore contains biodegradable reagent Polyamide article will not start biodegrade in the desired use of product described herein.In fact, biodegradable reagent is drawn Enter and cause higher biodegradation rate in biological poly nylon, while keeping making for textile application and in weaving Mechanically and chemically characteristic needed for fiber during the service life of product.In well-known waste management approach, biodegrade Process is aerobic or anaerobism carry out.
Fiber
Biodegradable Fypro according to the present invention advantageously has about 40 to 300 total decitex and about 1 to 5 Dpf (decitex/filament).Toughness (when fracture) is from 30 to 80cN/ dtex.Elongation (when fracture) is from 20% to 90%.
Method for obtaining biodegradable Fypro
The present invention also provides a kind of methods for obtaining biodegradable Fypro as described above.The party Method, which is related to squeezing out by melt-spun, is at least introduced into biodegradable reagent in Fypro.
According to the present invention, statement " melt-spun " is understood to refer to the polyamide of the melt form being converted to Fypro Extrusion process.One or more polyamide (expect grain, powder or melt form) can be fed in melt spinning apparatus.It should Method includes any conventional extruding spinning device polyamide extruded suitable for melt-spun, these devices are that those skilled in the art are ripe Know, such as single screw extrusion machine, double screw extruder, bi-component extruder and grid spinneret.The melt-spun squeezes out further It is defined as LOY (low orientated yarn), POY (partially oriented yarn), FDY (full drawing), FOY (being fully oriented yarn), LDI (low denier industry) or HDI (high danier industry).
According to preferred embodiment, melt-spun squeeze out the following steps are included:
A1. using polyamide as in melt, material grain or powder feed to the entrance of screw extruder
A2. make the molten polyamide, homogenize and pressurize,
A3. the polyamide of the melting is spun into fiber,
A4. the fiber is cooling and wind.
Wherein as pellet, powder or liquid form, it is preferable to use dosing devices during step a1 for the biodegrade reagent It is continually introduced into.
As mentioned above, which is preferably continually introduced into during the step a1 of single screw extrusion machine.It can Using by dosing device as metering pump or weight apparatus for feeding, preferred weight apparatus for feeding are as pellet, powder or liquid form It is added.Vector resin includes any polymer that is compatible with polyamide chemistry and allowing additive suitably to disperse.Most preferably, should Vector resin is made of polyamide 6, polyamide 66 and its mixture.According to this embodiment, before forming fiber, by the life Object degradation reagent is mixed with the polyamide melt.
In the method according to the invention, the biodegrade reagent is advantageously with the total weight of the Fypro by weight The amount of meter 1.0% to 5.0%, preferably 1.5% to 2.5% introduces.In especially preferred embodiment of the invention, the life Object degradation reagent is the total of the Fypro by means of the amount that weight apparatus for feeding is continually introduced into as pellet, and is added By weight the 2% of weight.
In step a2, by polyamide in the screw extruder, preferably in temperature (temperature from 260 DEG C to 310 DEG C Higher than the melting temperature of the polyamide) under and under from 30 to 70 bars of extrusion pressure melt, homogenize and pressurize.
Then, according to step a3, preferably from 260 DEG C to 310 DEG C at a temperature of, from 150 to 250 bars of filament spinning component pressure Under power and filament spinning component flow velocity from 3 to 8kg/h, using the spinning screen component containing filter element and spinneret, this is melted The polyamide melted is spun into fiber (or yarn or long filament).
Step a4 is that these cooling fibers (or yarn or long filament) are wound until cured form and by these Fypros The step of rolling up (bobbin) at spool.Spinning oil can also be added on fiber in this step.
In the present invention, extruder can be equipped with metering system, for will polymerize in step a1 and/or a2 and/or a3 Object and optionally additive such as Masterbatch are introduced into host polymer.
Additional additive can introduce during the method for the present invention, or can reside in polyamide and/or biology In degradation reagent.These additives are selected from: plasticizer, antioxidant, stabilizer such as heat or light stabilizer, colorant, pigment, at Core agent such as talcum, oil absorbent such as titanium dioxide or zinc sulphide, processing aid, biocide, viscosity modified dose, catalyst is remote red Outside line emit mineral, antisatic additive, functional additive, optical brightener, Nano capsule, antibacterial, anti-mite, it is antimycotic or its His conventional additives.In the polymer or in step a1 and/or a4 that melt-spun squeezes out, generally it is added by the polyamide article These additives of the amount of the 0,001% to 10% of poidometer.
Polyamide article
Then Fypro according to the present invention can be converted to polyamide article, particularly textile fabric and/ Or clothes.Polyamide article according to the present invention is preferably by of the invention or (definition is such as by obtaining according to the method for the present invention On) Fypro made of fiber, staple fiber, short flannel, braided fabric, knitted fabric or supatex fabric or textile system Product.
The textile fabrics can be any textile fabrics as known in the art, including but not limited to, Woven fabric, knitting Fabric, supatex fabric, rope, rope, sewing thread etc..
Method for obtaining polyamide article
For the Fypro to be transformed into polyamide article as the method for textile fabric or clothes is this field skill Known to art personnel.Really, Fypro can pass through Texturized, stretching, warping, knitting, braiding, non-woven processing, clothes It fills manufacture or combinations thereof and is transformed into polyamide article.Then these articles are used in extensive application, especially in carpet, small In carpet, upholstery, parachute, tent, bag, hosiery, underwear, gym suit, coat etc..
The processing and biodegradability of polyamide article
In one embodiment, when there is no compared with the identical object of reference of biodegradable reagent, this biological can be dropped The Fypro of solution is based particularly on the Fypro of PA5.6, in such as anaeroic digestor or anaerobism refuse landfill The biodegradation rate improved is shown in anaerobic environment.Biodegradable Fypro and the product being made from it with not Fypro containing biodegradable reagent has essentially identical shelf life and required characteristic with the product being made from it.Cause This, just starts biodegrade until material is contacted with anaerobic environment appropriate.The polyamide of this embodiment is by polyamide 5.X structure At X is from 4 to 16 integer.Most preferably polyamide 5.6.
In the second embodiment, when there is no compared with the identical object of reference of biodegradable reagent, this biological can be dropped The Fypro of solution shows the biodegradation rate improved in the aerobic environment of such as compost or soil.It is biodegradable Fypro and the product that is made from it and the Fypro without biodegradable reagent and the product tool being made from it There are essentially identical shelf life and required characteristic.Therefore, just start to give birth to until material is contacted with microorganism appropriate and environment Object degradation.The polyamide of this embodiment is made of polyamide 5.X, and X is from 4 to 16 integer.Most preferably polyamide 5.6.
The advantages of biodegradable Fypro according to the present invention and the product being made from it, is summarized as follows:
There is no biodegradable reagent, biodegradation rate is noticeably greater than the biology of same reference material Degradation rate, especially for PA5.6.
For PA5.X, it is significantly higher than according to the biodegradation rate that ASTM D5511 testing standard measures in biodegrade The biodegradation rate of fossil aramid fibers in the presence of reagent.
During the service life of textile fabrics, the mechanically and chemically characteristic of Fypro is constant.
When compared with conventional polyamide product, polyamide article shows higher biodegradation rate, causes shorter Life cycle and reduction processing problem.
Polyamide article can be obtained from renewable raw materials, to facilitate sustainable development and low environmental impact.
This method needs very small amount of biodegradable reagent, at low cost and be suitable for any routine and well-known Extrusion machinery.
Degradation only activates in the environment rich in microorganism, such as refuse landfill, digester or compost.
In view of examples given below, other details of the invention or advantage will be become more fully apparent obviously.
Detailed description of the invention
Fig. 1 is the curve graph of the biodegradability according to ASTM D5511 of the table 1 of following instance.
Example
It is formed a series of polyamide articles (embodiment 1 to 4), including comparison polyamide article (embodiment 3 and 4) and control Object (embodiment 2), and evaluate its mechanical property, photooxidation, biodegrade, renewable carbon content, IVN (Viscosity Index), ATG (end amido) and CTG (carboxyl end group).
Amino endgroup content (ATG)
Amino end group (ATG) content is determined by potentiometric titration.The polyamide of 2 gram quantity is added to the 90% of about 70ml In the phenol of wt.Hold the mixture in stirring and 40 DEG C at a temperature of being completely dissolved until the polyamide.Then this is molten Liquid is titrated at about 25 DEG C by 0.1N HCl.As a result equivalent/ton (eq/ tons) are reported as.In the feelings of analysis fiber and product Under condition, it is necessary to remove any residue or spin finish in advance.
Solution viscosity (IVN)
The determination of solution viscosity (IVN) is carried out according to ISO 307.The polyamide is dissolved in 25 with 0.005g/ml concentration In the formic acid of 90%wt at DEG C, and measure its flowing time.As a result it is reported as ml/g.
Carboxyl end groups content (CTG)
Carboxyl end group (CTG) content is determined by titration.The polyamide of 4 gram quantity is added in the benzyl alcohol of about 80ml. Hold the mixture in stirring and 200 DEG C at a temperature of being completely dissolved until the polyamide.Then the 0.1N in spent glycol Potassium hydroxide titrates the solution.As a result equivalent/ton (eq/ tons) are reported as.In the case where analyzing fiber and product, it is necessary to pre- First remove any residue or spin finish.
Biodegrade of the ASTM D5511- in anaeroic digestor
ASTM D5511/ISO 15985: a small amount of test article is added in a large amount of high activity inoculums, the inoculum It is stabilized before biodegrade test starts.The inoculum is obtained by directly from high solid biogasification unit residual Excess or the residue composition obtained after anaerobic sludge dehydration.Optimum condition is provided, and by mixture batch fermentation.Measurement produces The volume of raw biogas simultaneously is used to calculate the biodegradable percentage based on carbon conversion.
The reproducible Bio-based content of ASTM D6866-
The biology base of product or renewable content are the amounts of biology base carbon in material, as total organic carbon in material or product Score weight (quality) or weight percent (quality).Deriving " Bio-based content " using ASTM D6866 is to be based on and radiation The property identical concept of carbon dating.This is by deriving the amount of radioactive carbon (14C) and modern reference standard in unknown sample The ratio of amount is completed.The ratio is reported as the percentage with unit " pMC " (percentage of contemporary carbon).If by dividing The material of analysis is the mixture of radioactive carbon and fossil-carbon (that is, without radioactive carbon) now, then the pMC value obtained is directly and sample The amount of biological material present in product is related.
Photooxidation ISO 105B06
This method measures effect of the artificial light in textile characteristic, and is intended to simulate the aging condition of day night.It is advising Under fixed period (such as 72 hours) and condition (45 DEG C, 60% relative humidity), product is exposed to artificial light (such as xenon arc Light fastness test lamp) in.In our current research, mechanical property is assessed before exposure and later.
Hygroscopicity
About 2 grams of samples are placed in weighing bottle, and dry 2 hours (the weight W3) at 105 DEG C.Then by the weighing bottle It is put into the climatic chamber under 20 DEG C and 65%RH 24 hours.The weight (weight W1) of sample is measured again.Then by the weighing bottle It is put into the climatic chamber under 30 DEG C and 90%RH 24 hours.The weight (weight W2) of sample is measured again.It is surveyed by following equation Measure hygroscopicity increment: MR1=(W1-W3)/W3, MR2=(W2-W3)/W3.Hydroscopicity difference is by Λ MR (%)=MR2- What MR1 was obtained.
Example of the invention-example 1- has the polyamide 5.6 of 2% biodegradable reagent
It is squeezed out by melt-spun and biological poly nylon is prepared by 5.6 pellet of polyamide and biodegradable reagent.
5.6 pellet of polyamide is from Kai Sai Biotechnology Co., Ltd (Cathay Biotech) with trade markIt can Commercially available polyamide.According to method disclosed herein measurement, IVN is that from 138 to 142, ATG is from 38 to 42, and CTG is From 65 to 75.
Biodegradable reagent is to come fromLLC, in trade markUnder it is commercially available.
The biodegrade reagent is used into weight apparatus for feeding as masterbatch pellet in the step a1 of single screw extrusion machine It is continually introduced into.In step a2, by polyamide blend in the screw extruder about 290 DEG C at a temperature of and about 50 bars It melts, homogenize under extrusion pressure and pressurize.Then, filament spinning component pressure and about 5kg/h according to step a3, at about 200 bars Filament spinning component flow velocity under, the polyamide blend of the melting is spun into multifilament yarn.In step a4, Fypro is blended Object solidification is simultaneously wound into spool volume with 4200m/min.By the biodegrade reagent with total polyamide blend in step a1 2% weight is continuously added.Simultaneously by the further Texturized line density at 1x80f68 dtex of the multifilament polyamide blend of acquisition It is knitted into fabric.
Case of comparative examples 2-is free of the polyamide 5.6 of biodegradable reagent
It is squeezed out by melt-spun and biological poly nylon is produced by 5.6 pellet of polyamide, similar to item described in example 1 Part, but it is free from biodegradable reagent.
Comparison example 3-has the polyamide 6 .6 of 2% biodegradable reagent
It is squeezed out by melt-spun as polyamide 6 .6 pellet and is tried with identical method described in example 1 and biodegrade Agent produces the Fypro based on fuel.It is raw in Rhodia (Rhodia) Poliamida e Especialidades Ltda Produce polyamide 6 .6 pellet.It is the nylon salt polymerization by mainly containing hexamethylene diamine and adipic acid.According to herein The method measurement of disclosure, IVN (Viscosity Index) is from 128 to 132, and ATG (amine end groups) is from 40 to 45.
Comparison example 4-is free of the polyamide 6 .6 of biodegradable reagent
It is squeezed out by melt-spun and the Fypro based on fuel is produced by polyamide 6 .6 pellet, be similar to described in example 3 Condition, but be free from biodegradable reagent.
The research of biodegradability ASTM D5511
Result after table 1-300 days
Fig. 1 shows the curve graph.
The research ASTM D6866 of Bio-based content
Table 2- biology base result
Research-ISO the 105B06 of mechanical property before and after photooxidation
Table 3- mechanical property
Contain and the research of the yarn property without biodegradable reagent
Table 4- yarn property
The Study on Hygroscopicity of polyamide
Table 5- hygroscopicity
20 DEG C of 65%RH 30 DEG C of 90%RH Hygroscopicity [increment]
PA 5.6 5.0% 10.1% 5.1%
PA 6.6 3.8% 6.9% 3.1%
Conclusion
The biodegradability analysis (table 1) of ASTM D5511 is shown, and biodegradable reagent is in 300 days by biological poly The biodegradability of amide 5.6 improves at least 15.5%, and if it is considered that same growth rate, can in 5 years or 90% is predicted as in the shorter time.The biodegradability of enhancing is enough to substantially reduce environment influence without influencing polyamides The primary characteristic of amine.Therefore, Biodegradation Times are unexpectedly from > 50 years (the expection Biodegradation Times of original polyamide) It reduces to down to 5 years or shorter.
Polyamide 5.6 discloses the positive cooperativity with biodegradable reagent, has in the presence of the reagent more poly- than conventional Higher biodegradable rate (high 11.5%) of amide 6.6.
About bio-based carbon content, example of the invention (example 1) clearly confirms that renewable carbon really more than 40% (table 2), and compare polyamide 66 sample be zero, it means that the carbon of polyamide 5.6 be biology base rather than PA 6.6 based on Fossil fuel.
Table 3 and table 4 do not show the significant decrease of chemistry and mechanical property.Such as the polymer features of viscosity and end group Keep identical, it means that can dyeability, toughness and elongation be not affected by and significantly affect.

Claims (24)

1. a kind of biodegradable Fypro, includes:
Polyamide at least 4% hygroscopicity increment,
Biodegradable reagent.
2. biodegradable Fypro according to claim 1, wherein the polyamide is selected from by the following terms group At group: polyamide 4, polyamide 4.6, polyamide 4.10；Polyamide 5.X, X are from 4 to 16 integers；Polyamide 6, polyamide 6.6, polyamide 6 .9, polyamide 6 .10；Polyamide 6 .12；Polyamide 10.10；Polyamide 10.12；Polyamide 11；Polyamide 12；Polyamide 12.12；And its mixture, on condition that these polyamide are modified if necessary to reach at least 4% hygroscopicity Increment.
3. biodegradable Fypro according to claim 1 or 2, wherein the polyamide is hydrophilic by being added Modifying agent, such as water-soluble polymeric image polyvinylpyrrolidone, sulfonate polar groups such as organic sulfonic acid；By making the polyamides Amine and ethylene oxide group or polyethers amine groups are copolymerized；Chemical modification is carried out by increasing the ratio of non-crystalline areas；Or pass through increasing Add fiber and the therefore surface area of water sucting surface, such as with the fibre structure for possessing high porosity and capillarity, into Row physical modification.
4. biodegradable Fypro according to any one of claim 1 to 3, wherein the polyamide is selected from The group being made of the following terms: polyamide 4, polyamide 4.6, polyamide 4.10；Polyamide 5.10；Polyamide 6, polyamide 6 .6, Polyamide 6 .9, polyamide 6 .10；Polyamide 6 .12；Polyamide 10.10；Polyamide 10.12；Polyamide 11；Polyamide 12；It is poly- Amide 12.12；And its mixture, they are by being added hydrophilic modifier, such as water-soluble polymeric image polyvinylpyrrolidone, sulphur Hydrochlorate polar group such as organic sulfonic acid；Or it is modified by being copolymerized the polyamide with ethylene oxide group or polyethers amine groups.
5. biodegradable Fypro according to claim 1 or 2, wherein the polyamide is polyamide 5.6.
6. biodegradable Fypro according to claim 5, wherein the polyamide is the polyamides not being modified Amine 5.6.
7. biodegradable Fypro according to any one of claim 1 to 6, wherein biodegrade examination Agent is deposited with the amount of by weight from the 0.5% to 5.0% of the total weight of the Fypro, preferably from 1.0% to 3.0% variation ?.
8. biodegradable Fypro according to any one of claim 1 to 7, wherein biodegrade examination Agent includes at least one of following components:
A. chemical inhibitor or chemotaxis compound,
B. glutaric acid or derivatives thereof,
C. carboxylic acid compound,
D. biodegradable polymer,
E. vector resin,
F. sweller.
9. biodegradable Fypro according to any one of claim 1 to 8, wherein biodegrade examination Agent includes the chemical inhibitor of the attraction microorganism selected from the group being made of the following terms: sugar, cumarin, furanone and its mixing Object.
10. biodegradable Fypro according to any one of claim 1 to 9, wherein biodegrade examination Agent includes glutaric acid or derivatives thereof, preferably propyl glutaric acid.
11. biodegradable Fypro according to any one of claim 1 to 10, wherein the biodegrade Reagent includes carboxylic acid, preferably hexadecanoic acid.
12. biodegradable Fypro according to any one of claim 1 to 11, wherein the biodegrade Reagent includes the biodegradable polymer selected from the group being made of the following terms: polylactic acid, poly- (lactic acid-ethanol) copolymerization Object, poly (propylene carbonate), polycaprolactone, polyhydroxyalkanoates, chitosan, glutelin and one or more aliphatic/fragrance Adoption ester, as poly butylene succinate, poly-succinic-tetramethylene adipate, poly-succinic-decanedioic acid butanediol ester or Polybutylene terephthalate (PBT)-be total to adipate ester, or mixtures thereof.
13. biodegradable Fypro according to any one of claim 1 to 12, wherein the biodegrade Reagent includes vector resin, which is or mixtures thereof polyamide 6, polyamide 66.
14. biodegradable Fypro according to any one of claim 1 to 13, wherein the biodegrade Reagent includes sweller, which is selected from the sense organ sweller of group being made of the following terms: natural fiber, culture glue Body, cyclodextrin, polylactic acid and its mixture.
15. according to claim 1 to Fypro biodegradable described in any one of 14, wherein the biodegrade Reagent includes the microorganism that can digest Fypro.
16. according to claim 1 to Fypro biodegradable described in any one of 15, wherein the biology can drop Solution property is in aerobic or anaerobism waste management approach, as obtained under anaeroic digestor, refuse landfill or compost environment.
17. according to claim 1 to Fypro biodegradable described in any one of 16, wherein the biology can drop Solution property obtains off field in anaerobic condition, such as anaeroic digestor or garbage loading embeading.
18. a kind of for obtaining such as biodegradable Fypro defined in any one of claims 1 to 17 Method, wherein the Fypro is squeezed out by the melt-spun of at least the following terms and obtained:
Polyamide at least 4% hygroscopicity increment,
Biodegradable reagent.
19. according to the method for claim 18, wherein the melt-spun squeeze out the following steps are included:
A1. using the polyamide as melt, material grain or powder feed to the entrance of screw extruder in,
A2. make the molten polyamide, homogenize and pressurize,
A3. the polyamide of the melting is spun into fiber,
It is a4. the fiber is cooling and wind,
Wherein, as liquid, pellet or powder type, it is preferable to use dosing device companies during step a1 for the biodegrade reagent Continue and is uniformly introduced.
20. a kind of polyamide article, comprising as defined in any one of claims 1 to 17 or by claim 18 or The biodegradable Fypro that method defined in any one of 19 obtains.
21. polyamide article according to claim 20, wherein the polyamide article is by such as in claim 1 to 17 Any one of defined in or as the method defined in any one of claim 18 or 19 obtain have enhancing Fiber made of the biodegradable Fypro of biodegradability, staple fiber, short flannel, fabric, knitted fabric or non- Woven fabric or textile fabrics.
22. the method for obtaining the polyamide article as defined in any one of claim 20 or 21, wherein such as in right It is required that defined in any one of 1 to 17 or as being given birth to as what the method defined in any one of claim 18 or 19 obtained The Fypro of object degradation passes through Texturized, stretching, warping, knitting, braiding, non-woven processing, clothes manufacture or its group It closes and changes.
23. the method for the polyamide article as defined in any one of claim 20 or 21 of degrading, wherein such as in right It is required that defined in any one of 1 to 17 or as being given birth to as what the method defined in any one of claim 18 or 19 obtained The Fypro of object degradation is in aerobic or anaerobism waste management approach, such as anaeroic digestor, refuse landfill or compost ring It is handled in border, preferably anaeroic digestor or refuse landfill.
24. the polyamide at least 4% hygroscopicity increment is combined with biodegradable reagent to improve polyamides prepared therefrom The purposes of the biodegradability characteristic of amine.
CN201680084979.2A 2016-04-04 2016-04-04 Biodegradable Fypro, the polyamide article for obtaining the method for such fiber and being made from it Pending CN109072490A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2016/000432 WO2016079724A2 (en) 2016-04-04 2016-04-04 Biodegradable polyamide fiber, process for obtaining such fiber and polyamide article made therefrom

Publications (1)

Publication Number Publication Date
CN109072490A true CN109072490A (en) 2018-12-21

Family

ID=56014643

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201680084979.2A Pending CN109072490A (en) 2016-04-04 2016-04-04 Biodegradable Fypro, the polyamide article for obtaining the method for such fiber and being made from it

Country Status (10)

Country Link
US (1) US20200299867A1 (en)
EP (1) EP3440243B1 (en)
JP (1) JP2019513911A (en)
KR (1) KR102609367B1 (en)
CN (1) CN109072490A (en)
BR (1) BR112018070352B1 (en)
ES (1) ES2926676T3 (en)
IL (1) IL261843B (en)
PT (1) PT3440243T (en)
WO (1) WO2016079724A2 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110644066A (en) * 2019-09-12 2020-01-03 中山尚洋科技股份有限公司 Biodegradable agent, biodegradable fiber and preparation method
CN110843308A (en) * 2019-11-27 2020-02-28 格域包装科技（江苏）有限公司 Biodegradable film, preparation method thereof and application thereof in air energy packaging material
CN111118662A (en) * 2019-12-18 2020-05-08 晋江市远祥服装织造有限公司 Biodegradable environment-friendly fabric and preparation method and product thereof
CN111139546A (en) * 2020-02-21 2020-05-12 江南大学 High-strength superfine polyamide 11 fiber and preparation method thereof
CN111206301A (en) * 2020-01-22 2020-05-29 华东理工大学 Preparation method of bio-based degradable polymer superfine fiber
CN111235674A (en) * 2020-02-13 2020-06-05 上海珈羽国际贸易有限公司 Degradable polyester fiber and preparation method thereof
CN111235688A (en) * 2020-03-19 2020-06-05 苏州市佩发刺绣工艺品有限公司 Biodegradable polyester fiber and preparation method thereof
CN111549423A (en) * 2020-03-23 2020-08-18 合肥利夫生物科技有限公司 Bio-based flame-retardant material
CN112126157A (en) * 2020-09-29 2020-12-25 汕头市国宏经贸有限公司 Petroleum-based biodegradable material and product thereof
CN112647312A (en) * 2020-12-09 2021-04-13 魔力薇薇(上海)服饰科技有限公司 Biodegradable glove and preparation method thereof
CN114196172A (en) * 2021-12-29 2022-03-18 扬州云翰塑料包装有限公司 Biodegradable low-carbon polymer packaging bag and preparation method thereof
CN114657659A (en) * 2022-03-31 2022-06-24 无锡沛莱斯纺织有限公司 Biodegradable elastic material and garment and preparation method thereof
CN115522294A (en) * 2022-09-20 2022-12-27 江苏集萃先进纤维材料研究所有限公司 Preparation method of bio-based antibacterial fancy yarn
CN115926154A (en) * 2022-12-30 2023-04-07 徐州天虹银丰纺织有限公司 Preparation method of polymer fiber for functional textile and textile fabric

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK3325703T3 (en) 2016-08-02 2019-10-28 Fitesa Germany Gmbh System and method for preparing nonwoven polylactic acids
US11441251B2 (en) 2016-08-16 2022-09-13 Fitesa Germany Gmbh Nonwoven fabrics comprising polylactic acid having improved strength and toughness
TWI722359B (en) * 2018-01-02 2021-03-21 美商普利馬洛夫特公司 Biodegradation-enhanced synthetic fiber and methods of making the same
CA3004436C (en) 2018-05-09 2021-06-01 Paige Whitehead Biodegradable light wand
US10683399B2 (en) 2018-06-26 2020-06-16 Intrinsic Advanced Materials, LLC Biodegradable textiles, masterbatches, and method of making biodegradable fibers
CN112267212A (en) * 2020-10-15 2021-01-26 深圳市通产丽星股份有限公司 Biodegradable polypropylene composite material, melt-blown non-woven fabric and application thereof
CN113429751A (en) * 2021-06-16 2021-09-24 山西兰花华明纳米材料股份有限公司 Biodegradable functional granules and preparation method thereof
CN114085509A (en) * 2021-11-29 2022-02-25 洛阳绿之汇塑料降解科技有限公司 Universal masterbatch for anaerobic digestion degradation and preparation method thereof
CN114213653B (en) * 2021-11-30 2022-08-23 东华大学 Polyamide and preparation method thereof
KR102519429B1 (en) * 2022-02-25 2023-04-11 주식회사 스포테크 Pile yarn for biodegradable artificial turf
KR102568630B1 (en) * 2022-05-30 2023-08-22 주식회사 스포테크 Biodegradable shock absorbing pad
JP2024060282A (en) * 2022-10-19 2024-05-02 国立大学法人高知大学 Use of filler, environmentally friendly plastic, environmentally friendly plastic fiber, and PGA ion complex

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1743516A (en) * 2005-09-16 2006-03-08 华南理工大学 Moisture-absorption modifier, and its preparing method and use in polyamide fiber
JP4256243B2 (en) * 2003-10-17 2009-04-22 ユニチカファイバー株式会社 Polylactic acid-based hydrophilic fiber
CN101589097A (en) * 2006-10-31 2009-11-25 生物科技环境公司 Chemical additives to make polymeric materials biodegradable
CN102834556A (en) * 2010-03-31 2012-12-19 东丽株式会社 Hygroscopic fibre, and manufacturing method for same
CN103668553A (en) * 2012-09-19 2014-03-26 东丽纤维研究所（中国）有限公司 Blend fiber and production method and application thereof
CN103668536A (en) * 2012-09-13 2014-03-26 东丽纤维研究所（中国）有限公司 Moisture-absorbing fiber and preparation method thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06322263A (en) * 1993-05-14 1994-11-22 Kuraray Co Ltd Biodegradable polymer composition and molded article
JP3554620B2 (en) 1995-10-16 2004-08-18 ユニチカ株式会社 Biodegradable bicomponent fiber having moisture absorption / release properties and its production method
JP3804097B2 (en) 1996-03-29 2006-08-02 東レ株式会社 Support stockings with excellent wearing comfort
WO2004013388A1 (en) * 2002-08-05 2004-02-12 Toray Industries, Inc. Porous fiber
CN1490443A (en) 2002-10-14 2004-04-21 金淑杰 Biodegradable fiber and producing method thereof
US7098292B2 (en) 2003-05-08 2006-08-29 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
JP2006132041A (en) 2004-11-08 2006-05-25 Toyobo Co Ltd Stocking
JP2006274482A (en) * 2005-03-29 2006-10-12 Toray Ind Inc Polyamide fiber and method for producing the same
JP5549244B2 (en) 2010-01-29 2014-07-16 東レ株式会社 Hygroscopic polyamide 56 short fiber
JP5454191B2 (en) * 2010-02-09 2014-03-26 東レ株式会社 Crimped yarn and fiber structure
IT1402747B1 (en) 2010-10-27 2013-09-18 Novamont Spa BIODEGRADABLE POLYESTER AND ADHESIVE FILMS FITTED WITH IT.
US20140003026A1 (en) 2012-07-02 2014-01-02 Omniglow, Llc Biodegradable chemiluminescent articles
BR112015004327A2 (en) 2012-08-30 2017-07-04 Showa Best Glove Inc biodegradable compositions, methods and uses thereof
US20150065650A1 (en) 2013-08-29 2015-03-05 Nylon Corporation Of America, Inc. Biodegradable nylon and method for the manufacture thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4256243B2 (en) * 2003-10-17 2009-04-22 ユニチカファイバー株式会社 Polylactic acid-based hydrophilic fiber
CN1743516A (en) * 2005-09-16 2006-03-08 华南理工大学 Moisture-absorption modifier, and its preparing method and use in polyamide fiber
CN101589097A (en) * 2006-10-31 2009-11-25 生物科技环境公司 Chemical additives to make polymeric materials biodegradable
CN103865288A (en) * 2006-10-31 2014-06-18 生物科技环境公司 Chemical Additives to Make Polymeric Materials Biodegradable
CN102834556A (en) * 2010-03-31 2012-12-19 东丽株式会社 Hygroscopic fibre, and manufacturing method for same
CN103668536A (en) * 2012-09-13 2014-03-26 东丽纤维研究所（中国）有限公司 Moisture-absorbing fiber and preparation method thereof
CN103668553A (en) * 2012-09-19 2014-03-26 东丽纤维研究所（中国）有限公司 Blend fiber and production method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAMES ROONEY: "含Eco-one的塑料的生物降解过程", 《有机添加剂ECO ONE 提高塑料的生物降解性能》 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110644066A (en) * 2019-09-12 2020-01-03 中山尚洋科技股份有限公司 Biodegradable agent, biodegradable fiber and preparation method
CN110644066B (en) * 2019-09-12 2022-09-16 中山尚洋科技股份有限公司 Biodegradable agent, biodegradable fiber and preparation method
CN110843308A (en) * 2019-11-27 2020-02-28 格域包装科技（江苏）有限公司 Biodegradable film, preparation method thereof and application thereof in air energy packaging material
CN111118662A (en) * 2019-12-18 2020-05-08 晋江市远祥服装织造有限公司 Biodegradable environment-friendly fabric and preparation method and product thereof
CN111206301B (en) * 2020-01-22 2022-08-12 华东理工大学 Preparation method of bio-based degradable polymer superfine fiber
CN111206301A (en) * 2020-01-22 2020-05-29 华东理工大学 Preparation method of bio-based degradable polymer superfine fiber
CN111235674A (en) * 2020-02-13 2020-06-05 上海珈羽国际贸易有限公司 Degradable polyester fiber and preparation method thereof
CN111139546A (en) * 2020-02-21 2020-05-12 江南大学 High-strength superfine polyamide 11 fiber and preparation method thereof
CN111235688A (en) * 2020-03-19 2020-06-05 苏州市佩发刺绣工艺品有限公司 Biodegradable polyester fiber and preparation method thereof
CN111549423A (en) * 2020-03-23 2020-08-18 合肥利夫生物科技有限公司 Bio-based flame-retardant material
CN112126157A (en) * 2020-09-29 2020-12-25 汕头市国宏经贸有限公司 Petroleum-based biodegradable material and product thereof
CN112647312A (en) * 2020-12-09 2021-04-13 魔力薇薇(上海)服饰科技有限公司 Biodegradable glove and preparation method thereof
CN114196172A (en) * 2021-12-29 2022-03-18 扬州云翰塑料包装有限公司 Biodegradable low-carbon polymer packaging bag and preparation method thereof
CN114657659A (en) * 2022-03-31 2022-06-24 无锡沛莱斯纺织有限公司 Biodegradable elastic material and garment and preparation method thereof
CN115522294A (en) * 2022-09-20 2022-12-27 江苏集萃先进纤维材料研究所有限公司 Preparation method of bio-based antibacterial fancy yarn
CN115522294B (en) * 2022-09-20 2024-02-27 江苏集萃先进纤维材料研究所有限公司 Preparation method of bio-based antibacterial fancy yarn
CN115926154A (en) * 2022-12-30 2023-04-07 徐州天虹银丰纺织有限公司 Preparation method of polymer fiber for functional textile and textile fabric
CN115926154B (en) * 2022-12-30 2023-10-27 徐州天虹银丰纺织有限公司 Preparation method of polymer fiber for functional textile and textile fabric

Also Published As

Publication number Publication date
IL261843A (en) 2018-10-31
BR112018070352B1 (en) 2022-09-06
EP3440243A2 (en) 2019-02-13
US20200299867A1 (en) 2020-09-24
KR102609367B1 (en) 2023-12-05
KR20180123578A (en) 2018-11-16
IL261843B (en) 2022-03-01
BR112018070352A2 (en) 2019-01-29
EP3440243B1 (en) 2022-06-22
WO2016079724A2 (en) 2016-05-26
ES2926676T3 (en) 2022-10-27
WO2016079724A3 (en) 2017-10-19
JP2019513911A (en) 2019-05-30
PT3440243T (en) 2022-09-16

Similar Documents

Publication Publication Date Title
CN109072490A (en) Biodegradable Fypro, the polyamide article for obtaining the method for such fiber and being made from it
JP7489336B2 (en) Methods for making biodegradable textiles, masterbatches, and biodegradable fibers
US20080042312A1 (en) Deep-dyeable modified polylactic acid fiber
JP4423882B2 (en) Polylactic acid fiber
US20120107527A1 (en) Use of polymer blends for producing slit film tapes
KR20070120115A (en) Resin composition, molded article produced from the same, and processes for production of the composition and article
JP2003514092A (en) Acid dyeable polyester composition
CN107002305B (en) Method for manufacturing toothbrush bristles containing biodegradable resin and toothbrush using same
JP3982305B2 (en) Polylactic acid fiber with excellent hydrolysis resistance
CN105040133A (en) Monofilaments with high abrasion and shape stability, low sliding friction and propensity towards soiling, textile planar structures containing the same, and the use of same
TW558570B (en) Polyester fiber
JP5441591B2 (en) Bending-resistant multifilament
JP2008184695A (en) Fiber aggregate
JP2000234217A (en) Spun-dyed polyester fiber
JP2005350829A (en) Polylactic acid fiber having excellent hydrolytic resistance
JPH08183898A (en) Polylactic acid composition and its molded product
KR102553049B1 (en) Biodegradable material, biodegradable fiber member, biodegradable fabric member and manufacturing methods thereof
Kılınç et al. The Production and Physical and Thermal Characterization of Polybutylene Succinate Multifilament Yarns
JP2010189807A (en) Spun-dyed aliphatic polyester staple fiber
KR20240073199A (en) Biogradable polyester composite yarn and manufacturing method thereof
Dutkiewicz et al. Method to produce biodegradable aliphatic-aromatic co-polyesters with improved colour
JP2024060618A (en) Use of filler, environmentally friendly plastic, environmentally friendly plastic fiber, and PGA ion complex
KR20230102477A (en) Biodegradable masterbatch composition and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20220415

Address after: Brazil, St Paul

Applicant after: RHODIA BRASIL Ltda

Address before: Brazil, St Paul

Applicant before: RHODIA POLIAMIDA E ESPECIALIDADES Ltda

TA01 Transfer of patent application right